Vat dyestuffs of the anthraquinone series



@30 ample alkali Patent ed Nov? 1933,"

vA'r DYESTUFFS Inc., New York, N. ware 'No Drawing. Application .lanu g 8,234, and in Germany January ducing same.

7 5 We have found thatvaluable vat dyestufl's are obtained by condensing -an anthraquinone acri done or, anthraquinone thioxanthone carboxylic acid or a substitution product thereof with an aromatic amine which is substituted in the 10 ortho-position to the aminogroup by an 0H,, SH'

or N02 groupor' halogen, whereby compounds of the general formula: Q

anthraquinone radical, X is an imino group-or.

a sulphur atom and Y is asulphur or. oxygen atom are obtainedeitherdirectlyor bythe action of condensing agents on the i acyla'mines inter mediately produced. The condensation of the anthraquinone acridone oranthraquinone thioxanthone carboxylic acid or their substitution products withthe said aromatic amines is pref erably effected by heating the said substances together in solutionors'uspension if desired in the presence of condensing (agents, as for exmetal carbonate's,, acetatesand the like. As substitution products of the anthraquinone acridone or anthraquinone thioxanthone carboxylic acids may be-mentioned the chlorides, anhydrides and esters of the said acids.

The initial material may also be substituted in the anthraquinone nucleus of the said acridone and thioxanthonecarboxylic acids, thus they may be substituted'by halogen, alkyl, alkoxy, amino groups and amino groups in which a hydrogen atom is repaced by alk Thesame 'substituents may also be present in the aromatic amines. The condensation is preferably carried'out in high boiling inert; in par ticular aromatic solvents, such as nitrobenzene,

halogenbenze'nes andhomologues thereof, naphthalene, its homolo thereof.- The condensation is out at temperatures above 150? (3., since generally speaking, at these temperatures condensation and ring closure is simultaneously effected.

When by the condensation'an intermediate'product is formed it may be readily converted-into the said fin'al product-by ring closure by treatment with ccndensingagents. such as sulphuric acid, p-toluene-sulphonic acid, or alkali metal carbonates or acetates. When employing in the initial condensation aminescontaining a halogen atom ortho-position to the "amino" group,

yl, aryl or acylradicaISL gues and'halogen derivatives 1 preierably carried ch, Ludwigshafen 7 Stein, Mannheim,"

dry "22," 1932,

agents supplying, sulphur may.

the conversion of the A whereby thiazolesare obtained. The followingexamples will f the nature ofthis invention but not restricted to thes by weight. I

lOparjts of the chloride o f,1,2 one-thioxant (obtainable for 'exampl brom anthra'quinone' para-mercapto ben zoic uN osr rss PA ENT owl re sts on-the-Rhine, and Berthold Germany, assignors to General Aniline Works,

Y., a corporati gf 1 intermediate e examples. The parts are Lama 1 hone-' Bz' i-caifboxylic formulaij a g 0001 e by condensation or z- I l carboxylic acid with acidythioxanthone ring be employed in products,

urtherillustrate the invention is a l t. he

:clo'sure' by means of sulphuric acid and conversion into the carb thionyl' chloride C: with 7 part quinone in 170 vformation ofth dyestuffmay be cipitation from I treatment with cotton greenish sulphuric acid ness properties from a darkfviolet v "Example 20.2 parts of 1 2(S) thone-Bz2-carbo formula:

-anthraq (obtainable from -cyan-z-brdm ylic acid. chloride having the com. 1..

oxylic acid chloride by means. of

arelhe ated at fr m IQWtoZOQ" 1 s of I1-mercapto -2gaminoanthra-v :parts of nitrobenzene until the edyestuff; is completed. The purified by dissolution and pre andjsubsequent hypochlorite solutidnf. It dyes yellowshades' avin uinonethioxan f n hi ui pne one'ring closure 1 5 ride) are heated one-2-carboxylic acid with thios'alicylic acid, ef-i orange'crystals.

. the .vat of the product and V 2.1 (S)-anthraquinone-thioxanthone-Bze-caryellow shades from an olive brown ivat.

' Example-.3

2 parts of 2.1 (S) -anthraquinone-thioiranthone- Bz2-carboxylic acid chloride having the iormula:,

I .n V 0 (obtainablejj jcondensing' l-chlor-e anthraquin fecting ring closure. by means. of acetic anhydride with an addition of sulphuric acid and converting the product 11113041116 acid chloride by treatment with thionyl chloride in o-dichlorbenzene) are heated at 190 C. with 1.2 parts of 1- amino-2- hydroxy anthraq'uinone in 500 parts of trichlorbenzene until the formation of dyestuff has ceased. The dyestuff; which is diflicultly soluble even in hot solvents;' s'eparates-in the form of It is isolated in the usual manher and may be V ation from concentrated sulphuricacid. It dyes cotton yellow shades from a violet vat.

; In] av similar manner other oxazoles can be prepared fromithel components indicated in the following table'whichalsogives the colour of dyeings on cotton.

Dyei on cot- Colour ofthe F v ton Condensation product from Dark violet dro ryanthraquinone V 1.2 .(S) -ant hraquinonc-thioxanthone-B z4-,.car-

boxylic acid chloride and l-amino-Z-hydroxyanthraquinone Darkviolet Yellow 2.1 (S) -anthraquinone-thioxanthondBM-car- Violet boxylic acid chloride and 1-amino-2-l1yidroxyanthraquinone Orange 2.1 (S) anthmquinooe-thioranthone 6 car- Blue boxylic acid chlorideand 1-amin0-2-hydroxyanthraquinone Orange 3.2 (S)-anthraquinonethioranthone-Bz2car- Red-brown boxylic acid chloride and l-amino-Z-hydroxyanthraquinone Red to redbrown 3.2 (S) anthraquinone-thioxanthonerBzl-car- Yellow boxylic acid chloride and l-aminofl-hydroxyanthraquinone a Dark violet Orange boxylic acid chloride and Z-amino-S-hydroxyanthraquinone. i

3.2 (S)-anthraquinone-thioxanthone-Bz2rcar- Yellow boxylic acid chloride and 2-amino-3-hydroxyanthraquinone Brown Yellow- 3.2(S)-anthraquinoneethioxanthone-Bzi-car- .brown l Yellow purified if necessary by fractione the shades of their Yellow I Example 4 parts of 2.1 N)-anthraquinone-lf.2"(N)- naphthacridone-3-carboxylic acid chloride hav- *ing the formula: It is isolated in the usuaLmannerand.ifdesired I v r purified by a subsequent treatment with hypojchlorite solution. It dyes cotton'very greenish.

are heatedatirom 205? b01210? 'C. with 1.2 parts of..2amino-3 hydroxyanthraquinonein 400parts o'I" nitrocenze'ne until 'no" further increase in the amountof the difficultly soluble dyestufl. can be observed. The dyestuff, obtainedinfihe form of fine needles, is filtered by suction while hot and worked up in the usual-manner. It dyes cotton 7 reddish orange shades from a violet brown vat.

. a W5 20' parts 1 of 122KB) anthraquiirone thioxanthone Bz2-carboxylic acidfichloride cor'responding to theformula;

are heated with .13 parts of 1-ch1oro-2 -an 1inoan thraquinone and -300 parts of nitrobenzene to. i between 1190? and 195. C. until the-evolution of hydroge'nchloride has ceased. The mass is f1-ltered by suctionwhile stillhot and the reaction product which separates in the form; of yellow needles is- -ireed from nitrobenzene by washing. t

with ethyl alcohol. The product dyes cotton "from a green vat faintgreenish yellow shades. 2.9 parts of thisproductare heated in 55 parts of phenol with 6 parts of anhydrous ,sodiumsulphide and..9 partsoi sulphurto between m v and;. C, :until .the. 'product is free from chlo-V rine. The: reaction -mass is diluted with-ethyl f alcohol and the dyestuff v filtered ofie. bysuction, freedvfrom phenol by washing with'ethyl alcohol and treated with boiling sodium hypochlorite solution. It corresponds .inv its properties with thedyestuif described in Example 2. I InHasimilar. manner other thiazoles can be prepared .from the components indicated .inzthe following-table which alsogi-ves the colour-of 150 I chlorideL v v 1,936,949 I I thevatrofthe'product andithe'shades of'their calsofwhichat least'A orTBisiananthraquinone" dyeings on cotton. I s.

. Dyeing I Colour of Condensation product item the vat orzlot- 2.1 (S) l anthraquinonethioxanthone Red-violet Orange Bze-carboxylic acid chloride ,and l- I g mercapto-Z-aminoanthraquinone I I I 3.2 (S) anthraquinone thioxanthone Brown: I Yellow Bz2-carboxylic acid chloride and --1- I mercapto-Z-aminoanthraquinone 3.2 (S) anthraquincne thioxanthone Red-brown Reddish- Bz l-carboxylic acid. chloride and 1- yellow mercapto-2-aminoanthraquinone l I I 3.21 (S) anthraquinone t hioxanti Jone" R Yellowis' h- Yanb w Bz2-carboxylic 'acid chloride and obrown aminomercaptobenzene 2.1 (S)'- anthraquinone thioxanthone Violet Orange BzZ-carboxylic acid chloride and 1- mercapto-Z-aminoanthraquinone 3.2 (S) anthraquinone thioxanthone Brown Yellow I Bz3-carboxyie acid chloride and 1 mercapto-2-aminoanthraquinone I 2.1 (S) anthraquinone thioxanthone Blue violet Orange I 6 carboxylic acid chloride and 1 I mercapto-2-aminoanthraquinone 3.2 (S) anthraquinone thioxanthone Red-brown Yellow Bz i-carboxylic acid chloride and 1- amino-Z-mercapto-anthraquinone I The 3.2(S)-anthraquinone thioxanthone-Bzz carboxylic acid chloride is obtainable" by condensation of 2-chloranthraquinone 3-carboxylic acid with thiosalicylic acid in aqueous suspension to which caustic alkali has been added, effecting ring closure by means of sulphuric acidand converting the product into the carboxylic acid The 3.2 (S)-anthraquinone-thioxan thone-Bz4-carboxylic acidchloride isobtainabIe in thesaine' manner when using p-mercaptobenzoic acid insteadf'of thiosalicylic acid, and the cor-' responding Bz3-carboxylic acid chloride when employing m-mercaptobenzoic acid instead of thiosalicylic acid.

Example 6 38,7 parts of anthraquinone-2.1(N) -benzacrione-Bz i-carboxylic acid chloride are heated to boiling for 2 hour in 1500 parts of nitrobenzene with 24 parts of l-amino-2-hydroxy-anthraquin-' 1 clear brownish orange shades from a red violet vat.

What we claim is: 1. The process of producing vat dyestuffs, which comprises condensing an anthraquinone derivative selected from the group consisting of anthraquinone acridones and anthraquinone thioxanthones containing a carboxylic acid, carboxylic chloride or esterified carboxylic acid group, with an aromatic amine substituted in the ortho-position to the amino group by a substituent selected from the group consisting of halo- I gen, hydroxy, mercapto and nitro groups.

2. Vat dyestufls corresponding to the general I formula:

x Y o r N I;

;in which A, B and R stand for aromatic radimula: r

radical, X stands-for anaamina g'roupfior which dyestufis dye the vegetable fiber yellowf 1.80

to brown shades from red brown to violet vats.

3; 'Vat dyestufis corresponding to the general formula: i?

wherein the two Xs are yioinal members of an aromatic. radicle and. R corresponds to the forwherein one, Z stands ior C O, the other 2- :for'

a nitrogen or sulphur atom; and wherein the radical I I,

the vegetable fiber yellow tolbrownshades from;

red brown to violet vats.

' 4. Vat dyestufl's corresponding to the general formula;

wherein the two Xs areyici'nal members oi anj" aromatic radical and R. corresponds tothe formula: A I V wherein one Z stands for C=O, the other'Z fora I nitrogen or sulphur atom, and wherein the radical a is attached to two vicinal positions marked Y,

the other Y'being hydrogen, which dyestufi's dye rl t e v 1 GG949 v the vegetable :fiber yellow, torbrownshades @Imm HIThe "vatidyestuff' corresponding; to: the; for. redzbrowndzorviolet :vats. o v; mula: v t

Nat": dyestufis; corresponding vate. ztheugeneml formu1a:--l-, s y

. which dyest ff dyes cotton; greenish yellowlshades fromnrrolive btown'vat. v 9

V8."The vat-dyestu'fi corresponding toitha-iormula: In which Y stands for a. sulphur or oxygen atom, and the two Xs standfortwo vicinal carbon atoms of an anthraquinone radicaL'which dyestuffs dye cotton yellow shades from olive brown s I to violet vats.

6. The vat dyestuff corresponding to the formula-z, r e

which dyestuffs dyes cottonfrom ..a dark violet vat greenish yellow shades. iv V N 7 PAUL NAWIASKY.

v r r v Y Q I BERTHOLD STEIN. 11,15

.w 7 MILKRAI CH;

which-dyestuffs dyes cotton yellow shades .from ggda'lrkviolet vat v 

